Artificial mass and process of making same



Patented Jan. 15, 1935 an'rmcmr. Mass AND raocnss or G SAME HerbertHone], Klosterneuburg-Weidling, near Vienna, Austria,. assignor to Beck,Koller & Company, Inc., Detroit, Mich., a corporation of Delaware NoDrawing.

Original applications May 11, 1929,

Serial No. 362,460, and January 2, 1931, Serial N0. 506,296. Divided andthis application December 23, 1932, Serial No. 648,724. In Germany May6, 1928 Claims.

The invention relates to a process for producing organic masses of moreor less high molecular weight, which may be employed alone or incombination with filling materials as the basis 5 of pressed articles,as binding agents or for preparing varnishes and other coating orimpregnating agents and the like.

The present application is a division of my prior application Serial No.506,296, filed January 2, 1931, which latter application is a divisionof an earlier application Serial No. 362,- 460, filed May 11, 1929, nowPatent No. 1,800,296, which in turn is a continuation in part of myapplication Serial No. 218,587, filed Sept. 9, 1927, now Patent No.1,800,295.

The process consists in heating condensation products of low molecularweight, obtained with the aid of alkaline contact agents from suchphenolic substances, which possess only two particularly reactivepositions in the molecule and which, when heated alone change into aninfusible condition, to elevated temperatures together with anyester-like chemical substances. The reaction is accompanied with theformation of water and is to be regarded as a condensation reaction.

The present application relates more particularly to reacting thosecondensation products with mixed esters such as are obtained byesterifying carboxylic acids (polybasic or both polybasic and monobasic)on the one hand with both polyhydric and monohydric alcohols on theother.

As the particularly reactive positions in a phenol are to be regarded,as is known, the two ortho and the para positions to the phenolhydroxyl.One of these positions must therefore be occupied by a substituent.Examples of the latter are, a. hydrocarbon radical (alkyl, aryl,aralkyl, hydroaromatic radical) or an oxalkyl radical or chlorine. Othersubstituents have proved to be less suitable. One or both of the metapositions may on occasion also be occupied. The following are examplesof a few easily obtainable phenolic bodies of this kind: and p-cresol,certain xylenols, carvacrol, thymol; p-tertiary butyl phenol and amylphenol, p-benzyl phenol, as well as the corresponding derivatives ofm-cresol, guaiacol, oand p-chlorophenol, oand p-chloro-m-cresol, etc.

Derivatives of the dioxybenzenes, i. e. divalent m'ononucleur phenolicsubstances, are also suitable; the conditions, however, are somewhatmore complicated and not quite clear. As,

moreover, the use of these substances is lacking in economy they willnot be further discussed.

On the other hand, the applicability of all those di-valent, dienucleurphenolic substances, which are derivatives of thepp-di-oxy-diphenylmethane, is to be emphasized. They are easilyobtainable and result from the condensation of 2 mols of phenols orcertain homologues with 1 mol of a carbonyl compound with the aid ofhydrochloric acid, or, if possible, other acids. In the present case,the most suitable phenol homologue is o-cresol, from which di-ocresylolmethane, ethane, propane, or butane, is obtained according to whethercondensation has been effected with formaldehyde and its homologues oracetone and its homologues. Cyclic ketones may also be employed, inwhich case, for example, di-o-cresylol cyclohexane or di-o-cresylolmethyl-cyclohexane corresponding to the above compounds, are obtained.Phenol, however, may also be used as starting material, and, forexample, 2 atoms of chlorine be introduced as substituents, in thedi-phenylol compounds' thus obtained. In all these cases dinucleurdi-valent phenolic substances are obtained, all of which also onlypossess two reactive positions in the molecule.

It is to be observed that condensation products from phenolic substanceswith only one reactive position in the molecule may also be employed.The product resulting from the reaction of such substances with theneutral esterlike bodies is rather poor in quality and the yield israther limited, which is in agreement with the fact that, when heatedalone, they cannot be converted into the infusible state. Phenols ofthis kind are, for example, certain xylenols, pseudo-cumenol, creosol,chlor-o-cresol and chlor-p-cresol.

aand B-naphtol behave in a surprising manner like the last mentionedphenols, although they actually belong to the first mentioned group.

My invention more particularly consits in that where a substantiallyneutral ester-like body is reacted with a condensation product of theheathardening type and of low molecular weight obtained by alkalinecondensation from an excess of formaldehyde and a phenolic body, whichphenolic body has only two unsubstituted particularly reactivepositions, a smooth reaction mass may be obtained, as contrasted with alumpy mass containing insoluble and infusible particles, such as wouldresult where condensation products of the heat-hardening type areemployed, derived from phenols having all three particularly reactivepositions unsubstituted.

The mechanism of the reaction very probably is that the molecules of thecondensation product do not only react with one another leading to theformation of products of very high molecular weight, but also with theester-like substance or with its components. The alcoholic hydroxylgroups of the condensation product, known as very reactive, may bringabout unions so that multivalent ester components may be in part formed.This possibility in conjunction with the first mentioned reaction maylead to the formation of individual gelatinous or rubber-like infusibleand insoluble but nevertheless homogeneous masses. Such products arealso to be considered as being of infinitely high viscosity. Whenemploying smaller proportions of the condensation product a stillsoluble end product may be obtained which, however, also isdistinguished by an essentially higher viscosity as compared with thereaction mixture before entering the reaction, or with any of the twocomponents.

In general all possible ester-like substances have proved to beapplicable to the reaction. Even low molecular completely crystalloidesters, for example benzoic acid esters of monovalent alcohols, yieldaccording to the proportions employed, thin to highly viscous oils orgelatinous masses. Esters of monovalent alcohols with polyvalentcomponents may yield, even with lesser quantities of the samecondensation product, gelatinous end products. The full value of theprocess, however, is only reached when the ester-like substance is onewhich is practically non-volatile. Thus products which have beenobtained by esterification of a suitable mixture or both polyvalent andmonovalent ester-forming components are very advantageous in this sense.Also such esters are well adapted which are obtained from a polyvalentester-forming component on the one hand (e. g. a polybasic acid) and amixture of polyand monovalent components on the other side (e. g. amixture of polyand monohydric alcohols).

In order better to understand this, the wellknown fact may be mentionedthat the esterification of equivalent proportions of polybasic acids andpolyhydric alcohols in most cases finally leads to insoluble andinfusible masses. But when a sufllcient proportion of a monovalentester-forming component is employed simultaneously, the ester-likesubstance obtained is soluble and far from a rubber-like infusiblecondition. With such esters even small quantities of a condensationproduct produce the above described eflect.

The final end product obtained according to this process with a suitableproportion of a condensation product, shows very similar externalproperties to those of a mere ester obtained with a comparatively highproportion of the usually expensive polybasic acids, 1. e. it is stillsoluble but has a high viscosity and a certain rubberlike elasticity.The economic advantage of the process which enables the proportions ofpolyvalent ester components to be replaced to a very considerable extentby the usually cheap monobasic acid is thus very evident, the more so asat the same time a considerable saving in polyvalent alcohol is alsoeffected. Furthermore, such products obtained according to this processhave been found to be technically superior to merely ester-like productsor products otherwise equivalent as to viscosity conditions due to theirbetter waterproofness and generally greater resistance to chemicalinfluences.

It is, moreover, not necessary to start with the individual componentsof the esters as such; it is also possible to replace the monobasicacids (for example higher fatty acids etc.) wholly or in part by theirglycerides (i. e. fat or fatty oil), in which case individual esters arenevertheless obtained apparently owing to re-esterification. Purelyphysical mixtures of complicated esters of this kind and ordinary fattyacid glycerides, etc., may of course also be subjected together to thereaction with the condensation products. In such cases as these theeconomic advantage is, of course still greater.

The monobasic as well as the polybasic acids may be aliphatic, saturatedor unsaturated, aromatic or hydroaromatic, they may or may not containalcoholic or phenolic hydroxyl groups (i. e. they may or may not be oxyacids). Glycerine is the most important example of a polyvalent alcohol;alcohols of higher valency or the only divalent glycol may, however,also be employed.

Finally it should be again emphasized that esters of every kind may beemployed for the reaction. The hydroxyl compound may also be a phenoland the acid an inorganic acid. A condition for the success of thereaction is merely that the condensation product is soluble in theester-like substance (at least when hot) before a condensation reactiontakes place, as otherwise, of course, no mutual reaction can result.This result is obtained by suitably choosing the substituents in thephenolic substance. It may in some cases be convenient for instance ifthe ester-like compound is per se a resin-like substance of high meltingpoint to carry out the process in the presence of a suitable solvent;the latter may, if required, be removed by distillation when thereaction is over.

The preparation of the condensation products is effected in knownmanner, preferably by leaving the phenolic substance or a mixture ofseveral phenols and aqueous formaldehyde together, with at least so muchalkali hydroxide, that a clear solution results, if necesasry with theaid of alcohol, to react for a long time at room temperature or slightlyelevated temperature. The resulting reaction product is thenprecipitated with acid-reacting agents. Formaldehyde in excess of theequimolecular quantity is to be employed for successfully carrying outthe further reaction with the ester-like products.

This reaction may be effected in different ways. The quantity ofcondensation product employed may be such that, if the condensationreaction with the ester were carried to completion an insoluble,rubber-like product would result, in which case the reaction must beinterrupted before completion, if necessary even in its initial stage.In this case' the solutions of the resulting products yield coatings,which become particularly hard at furnace temperatures. If necessary,driers may also be added to the reaction product.

ing from an interrupted reaction are also particularly suitable for useas plastic masses. They may be employed with or without fillingmaterials for the preparation of various commodities.

An alternative procedure is to employ Products of this kind result:

condensation product in such aquantity that even on completecondensation with the esterlike product a viscous or resin-like,occasionally a wax-like end' product is obtained, which more or lessapproaches the rubber-like condition without actually attaining it.- Anincrease in the colloidal condition, such as in viscosity, is at leasteffected. In the case of solid, resin-like esters, an increase of theirmelting point is, as a rule, effected as well. The heating of theproduct can in this case be carried to about 200-220 C. for any desiredtime without any noteworthy further increase of the colloidal conditionbeing observed. The still soluble products or their solutions may beemployed alone as the basis for paints or, in general, as raw materialsfor the production of varnishes and other coating masses. If the acidcomponents or one of these components is derived from drying orsemidrying oils a drier may also be added, and in this way tough andhard drying varnishes may be obtained.

In individual cases very special eflects may also be obtained by meansof the process. Thus, for example, woo'd'goil, even when condensed withonly a small quantity of a suitable condensation product, loses itsknown disadvantageous manner of drying. A particularly hard, smooth andrapidly drying varnish may in fact be obtained in this way.

The invention will be more clearly understood by reference to thefollowing examples, which, however, are intended as illustrative only,rather than as restrictive.

EXAMPLES Example 1 6 parts of melissic palmitate (bees wax) are meltedand stirred up with the liquid condensation product obtained from onepart of ptertiary-amyl phenol and one part of 30% formaldehyde. Thetemperature is then gradually raised to 240 C'. The brown end productshows characteristic properties which differ from those of the bees waxitself. It is harder, more easily polished, more plastic and in thinlayers more transparent, and when poured out in thin plates iselastically pliable. When poured onto a smooth surface it displaysconsiderable adhesive powers. In general the colloidal properties of theproduct are considerably increased, and the product itself to a certainextent assumes resin-like properties.

Example 2 4 parts of melted beef tallow are stirred up with the viscouscondensation product resulting from 1 part of p-tertiary-butyl-m-cresoland 1 part of formaldehyde 40% by volume gradually heated up to 190 C.and maintained for 1-l hours at this temperature. The end product hasthe character of a very viscous oil and only sets when cooled with iceto a lard-like mass.

Example 3 grms. of castor oil and the crystalline condensation productobtained from 40 grms. of pcresol and 60 grms. of 30% formaldehyde areheated with stirring up to 180 C. and maintained at this temperatureuntil a cooled sample shows rubber-like elastic properties. The productis soluble in benzene and benzene-alcohol mixtures, as well as invarious other solvents, but not in alcohol alone. When mixed with asiccative a varnish is obtained which on drying becomes considerablyhard. The product may also be added as a softener to other siccativefreevarnishes.

Example 4 lent properties which dries clear extremely rapidly.

Example 5 A viscous condensation product obtained with the aid of alkalifrom 30 grms. of thymol and 40 grms. of 30% formaldehyde is introducedinto and dissolved in 500 grms. of a moderately boiled mixture of woodoil and linseed oil. This mixture, so-called honey-oil, is prepared inthe usual manner by heating a mixture of 1 part of wood oil and 3 partsof linseed oil for 4 hours at 280 C. It is to be regarded as the mixedglycerine ester of monobasic olefine carboxylic acids and polybasicolefine carboxylic acids obtained by partial polymerization. Thetemperature is gradually raised whilst stirring. After expelling themechanically combined water the reaction mixture is clear even whencold. It is finally heated up to 220 C. The product is still soluble andwhen cold represents a sticky and very ropy mass. On adding a siccativea fairly hard and tough drying varnish is obtained.

Example 50.

The quantity of honey-oil in the foregoing example is diminished to 300grms. and the reaction mixture only heated to 160 C.

The highly viscous oil, when suitably diluted, yields a coating agent(binding agent, impregnating agent, etc.) which even without theaddition of a siccative or without absorbing oxygen from the air yieldson heating to ISO-200 C. a tenaciously adhesive coat etc. For thisprocess 1 hour to 10 minutes are required according to the temperatureemployed. With the addition of siccatives a coat of pre-eminent hardnessand resisting power is obtained at this temperature.

Example 6 A condensation product of low molecular weight obtained from70 grms. of o-cresol and 100 grms. of 30% formaldehyde is dissolved withheating in 200 grms. of tricresyl phosphate and the mixture heated to160 C. until a sample on cooling shows a highly viscous ropy oil. It issoluble in benzene hydrocarbons and other solvents. It may be employed,for example, as the basis for furnace-drying varnishes. 0n continuedheating of 160 C. or higher a rubberlike to wood oil gelatinous mass isobtained.

Example 7 V 100 grms. of succinic acid, grms. of lactic acid (100%) and120 grms. of glycerine (98%) are heated to -200" C. until a softresin-like product with an acid number of about 25 is obtained. At about100-120 C. the crystalline condensation product obtained from 30 grms.of

p-chlorophenol and 35 grms. of 30% formalde-' Example 8 A condensationproduct'resulting from 55 grms. of p-chlor-m-cresol and 55 grms. offormaldehyde (40% by volume) is added with heating to the fairly hardand brittle resin-like esteriilcation product prepared as in Example '7from grms. of succinic acid, 160 grms. of salicylic acid and 100 grms.of glycerine and the mixture caused to react by raising the temperatureto about 200 C. Without an apparent increase in the melting point of theresin-like product being observed a resin of marked shellac-likeproperties is obtained. The resin-like condition in this case is withoutdoubt very considerably increased. The product is soluble in acetone andother solvents and may be employed for preparing polishes and the like.Its solutions may further be mixed with both nitrocellulose and withacetylcellulose varnishes. In both cases clear, satisfactorily adheringfilms are obtained.

Example 9 The ester-like semi-liquid reaction product obtained from 150grms. of citric acid (crystalline), 100 grms. of ricinoleic acid, 100grms. of salicylic acid and grms. of glycerine on the one hand and 45grms. of p-cresol di-alcohol on the other hand are caused to reacttogether at about 180 C. A soft, very tenaciously elastic pale resin isobtained, which is soluble in alcohol up to the proportion of 1:1, butsoluble in benzene-alcohol mixtures, in acetone, as well as inester-like solvents in any proportion. It is especially suitable asaddition to nitro-cellulose varnishes.

Example 10 The condensation product obtained as in Example 6 iscondensed with the thick oily ester obtained from 100 grms. of phthalicanhydride, 100 grms. of oleic acid and 65 grms. of ethylene glycol. Asoft, rubber-like, elastic resin is obtained, which is soluble inbenzene hydrocarbons as well as other solvents and is very suitable asan addition to nitrocellulose varnishes.

Example 11 The condensation product resulting from 3 parts of xylenol(124:5) and 4 parts of 30% formaldehyde is added to an ester having anacid number of 30 and obtained from 8 parts of d-tartaric acid, 4 partsof benzoic acid and 4 parts of ethylene glycol. A soft soluble resin,which is elastic like rubber, is obtained as in Example 10.

Example 12 action product is a mixture of o-cresol anddi-ocresylol-butane. It is condensed at room temperature with 100 grms.of formaldehyde (40% by volume) with the aid of caustic soda and thecondensation product precipitated with acid after about two weeks.

300 grms. of the ester-like product and half of the condensation productobtained above are heated together to 230 C. The resulting productrepresents at about 35 C. a soft elastic resin-like transparent mass.Even on cooling to room temperature it is first clear and elasticallyflexible. After a few hours it merely becomes translucent and is thenfairly brittle and easily friable. It is soluble in benzenehydrocarbons. Its solutions, when poured out in thin layers, allow thesolvent easily to evaporate. The layer of product which remains is firstclear, but after some time becomes cloudy likewax and possesses to ahigh degree the power of repelling water.

Example 13 220 grms. of the ester-like product obtained as in example 12are heated to C. with the remaining half of the condensation productobtained in the same example, until a cooled sample shows propertiessimilar to those of the end product obtained as in Example 12. Theproduct like the latter is soluble in benzene and the like. Thesolutions yield a temporarily clear film, which may be hardened at150-200 C.Yand which adheres well to the coated surface, possessesstrong water-repelling powers and remains permanently clear. The productitself, mixed with filling agents of any kind, may be employed forpreparing compressed substances.

Ezample 14 The ester of acid number 10 obtained from 50 grms..of sebacicacid, 100 grms. of technical abietic acid and 30 grms. of glycerine andwhich represents a soft sticky resinous mass, is worked up in the usualmanner with the crystalline oily condensation product obtained from 13grms. of guaiacol and 18 grms. of 30% formaldehyde. A resin somewhatsofter than shellac is obtained, which, at the temperature of itsmelting point, is elastic like rubber. It is soluble in benzenehydrocarbons, acetone, etc., and miscible to a clear solution withnitrocellulose in any proportion.

Example 15 2 parts of o-cresol and 1 part of technicalmethyl-cyclohexanone are condensed with the aid of hydrochloric acid.The reaction product consists of three isomers of di-o-eresylol-methyLcyclohexane CHLCGHQ (CH3.CsH3OH) 2 acid, 250 grms. of abietic acid and65 grms. of

glycerine and which represents a fairly brittle resin with an acidnumber of 20 and a melting point of 75-85 C. On condensing the latterwith the condensation product, a very hard resin melting about 30 C.higher is obtained.

mass. It is soluble in benzene hydrocarbons and yields clear films whenmixed with nitrocellulose.

Example 16 (a). 76 grms. of benzyl chloride are slowly added with gentleheating at the start to 108 grms. of technical m-cresol containing 60%of pure m-cresol. In the simultaneous presence of a catalyst consistingof about 5 grms. of dry zinc chloride the reaction starts fairly quietlyand may, if necessary, be later assisted and brought to completion byagain heating. The benzyl group merely enters the m-cresol as asubstituent with the removal of H01, most probably in the para position,possibly also in the ortho position. According to the work of Beilstein,the position of the benzyl group is not known. The p-cresol apparentlyremains untouched. The oily reaction product is repeatedly washed withhydrochloric acid-containing water and then 180 grms. of 30%formaldehyde added together with so much caustic alkali that aftershaking clear solution results. After about two weeks the condensationproduct is precipitated.

(b). 250 grms. of alcohol-soluble manila are melted at 230-240 C. with1000 grms. of colophony, and, if necessary, the melt freed from dirtparticles by filtration through a flne sieve. The mixture is thenesterified at a temperature of 240-280 C. with 150 grms. of glycerine(sp. g. 1.23).

Manila copal contains polybasic resin acids.

The condensation product is gradually introduced at 170 C. into thismixed ester and the temperature then raised to 250 C. The end product ishard and tough and readily soluble in drying oils.

Example 17 The thick oily esterification product obtained from 4 partsof phthalic anhydride, 6 parts of linoleic acid, 2 parts of colophonyand 3 parts of glycerine are heated to 150 C. with the condensationproduct obtained from 2 parts of butyl phenol and 2 parts of 30%formaldehyde until a sample when cold represents a soft rubber-likeelastic mass. The product is not only soluble in benzene hydrocarbons,but also in oil of turpentine and mineral spirits and yields, with orwithout the addition of siccatives, a varnish which dries very hard atfurnace temperature.

4-5 parts of linoleic acid employed for the above ester may be replacedby linseed oil. It only takes considerably longer until a uniformlyclear reaction mass is formed.

Example 18 The thick oily esterification product having an acid numberof 30 obtained from 50 grms. of phthalic anhydride, 150 grms. ofricinoleic acid and 50 grms. of mannite, is condensed at 180 C. with thecrystalline condensation product obtained from 30 grms. of a mixture ofoand pchlor-m-cresol and 30 grms. of formaldehyde (40% by volume). Themixture of phenolic substances is obtained by chlorinating the mcresoldissolved in glacial acetic acid with the calculated quantity ofelementary chlorine with ice cooling, and consist mainly of the paracompound.

The end product is very soft and elastic like rubber, it may be dilutedto a limited extent with alcohol, in any proportion with benzenehydrocarbons and ester-like solvents, and may be employed as an additionfor nitrocelluose varnishes. With the addition of siccatives it yields ahard drying varnish.

Example 19 The soft sticky esterification product obtained from grms. ofphthalic anhydride, 100 grms. of methyl cyclohexanol and 30 grms. ofglycerine is heated to 140-200 C. together with a condensation productresulting from 50 grms. of dichlor-di-phenylol-propane and 60 grms. of30% formaldehyde. A resin-like product, somewhat softer than shellac,results, which, like the latter has rubber-like elastic properties atthe temperature of its melting point. It can with advantage be employedas a resin for nitrocellulose varnishes- Example 20 grms. ofcrystallized citric acid, 200 grms. of benzyl alcohol are heatedtogether in a distillation flask until a temperature of 250 C. isreached. The benzyl alcohol distilled over with the water ofcrystallization and reaction is separated therefrom, re-introduced intothe flask, the above described operation being then repeated. Finallythe unchanged benzyl alcohol is removed by applying a vacuum. Thereaction product, which remains in the flask, amounts to about grms. andhas an acid number of 90-100; about 25 grms. of water are collected inthe receiver. That means that one carboxylic group has been esterifledand partial formation of anhydride has taken place. 50 grms. of oleicacid and 42 grms. of glycerine are now added and the whole is heated to250 C. until an acid number of 10 is reached. The light brown product isa thick liquid having the consistency of a thick boiled linseed oil.

The condensation product obtained as described in Example 18 isincorporated at a temperature below C., the temperature being thengradually raised up to 220 C. The final product is a resin, which issoft at ordinary temperature, of rubber-like elasticity, soluble inbenzene hydrocarbons, ester-like solvents and so on, and may be added tonitrocellulose varnishes in any desired proportion.

In the following claims the expression soluble artificial massesisintended to designate bases for coatings of all kinds, particularlyvarnishes, and bases for impregnating agents, binders and for all sortsof commodities.

The acids and their anhydrides are to be con-. sidered as equivalent informing the esters.

What I claim is:

1. A process of producing soluble artificial resinous masses whichcomprises reacting together (1) an excess of a product obtained byesterifying carboxylic acids with both monohydric and polyhydricalcohols and (2) a neutralized con densation product obtained with theaid of an alkaline catalyst from formaldehyde in excess of theequimolecular proportion and a phenol having only two unsubstitutedparticularly reactive positions in the molecule, the condensationproduct being capable of undergoing substantial further condensationwhen heated.

2. A soluble artificial resinous mass produced by reacting together (1)an excess of a product Obtained by esterifying carboxylic acids withable of undergoing substantial further condensation when heated.

3. .A process of producing soluble artificial resinous masses whichcomprises reacting together (1) the product obtained by esterifyingpolybasic carboxylic acids with both monohydric and polyhydric alcoholsand (2) a neutralized condensation product obtained with the aid of analkaline catalyst from formaldehyde in excess of the equimolecularproportion and a phenol having only two unsubstituted particularlyreactive positions in the molecule, the condensation product beingcapable of undergoing substantial further condensation when heated.

4. A soluble resinous mass produced by reacting together (1) the productobtained by esterifying polybasic carboxylic acids with both monohydricand polyhydric alcohols and (2) a neutralized condensation productobtained with the aid of an alkaline catalyst from formaldehyde inexcess of the equimolecular proportion and a phenol having only twounsubstituted particularly reactive positions in the molecule, thecondensation product being capable of undergoing substantial furthercondensation when heated.

5. A process of producing artificial solubleresinous masses whichcomprises reacting together (1) in excess of a product obtained byesterifying phthalic anhydride with both monohydric'and polyhydricalcohols and (2) a neutralized condensation product obtained with theaid of an alkaline catalyst from formaldehyde in excess of theequimolecular proportion and a phenol having only two unsubstitutedparticularly reactive positions in the molecule, the condensationproduct being capable of undergoing substantial further condensationwhen heated;

6. A soluble resinous mass produced by reacting together 1) an excess ofa product obtained by esterifying phthalic anhydride with bothmonohydric and polyhydric alcohols and (2) a neutralized condensationproduct obtained with the aid of 'an alkaline catalyst from formaldehydein excess of the equimolecular proportion and a phenol having only twounsubstituted particularly reactive positions in the molecule, thecondensation product being capable of undergoing substantial furthercondensation when heated.

7. A process according to claim 1 in which the phenol is a derivative ofthe binuclear divalent dihydroxy-diphenyl-methane and has only twounsubstituted particularly reactive positions while the other two suchpositions are substituted by chlorine.

8. A soluble resinous mass according to claim 2 in which the phenol is aderivative of the binuclear divalent dihydroxy-diphenyl-methane and hasonly two unsubstituted particularly reactive positions while the othertwo such positions are substituted by chlorine.

9. A process of producing soluble artificial resinous masses whichcomprises reacting together (1) the product obtained by esterifyingphthalic anhydride with both methyl cyclohexanol and glycerine and (2) aneutralized condensation product obtained with the aid of an alka linecatalyst from formaldehyde in excess of the equimolecular proportion anddi-chlor-diphenylo1 propane, the condensation product being capable ofundergoing substantial further condensation when heated.

10. A soluble resinous mass produced by reacting together (1) theproduct obtained by esterifying phthalic anhydride with both methylcyclohexanol and glycerine and (2) a neutralized condensation productobtained with the aid of an alkaline catalyst from formaldehyde inexcess of the equimolecular proportion and di-chlor-diphenylol propane,the condensation product being capable of undergoing substantial furthercondensation when heated.

11. A process of producing soluble artificial resinous masses whichcomprises reacting together (1) an excess of a product obtained byesterifying both polybasic and monobasic carboxylic acids on the oneside with both polyhydric and monohydric alcohols on the other side and(2) a neutralized condensationproduct obtained with the aid of analkaline catalyst from formaldehyde in excess of the equimolecu: larproportion and a phenol having only two unsubstituted particularlyreactive positions in the molecule, the condensation product beingcapable of undergoing substantial further condensation when heated.

12. A soluble resinous mass produced by reacting together (1) theproduct obtained by esterifying polybasic carboxylic acids with bothmonohydric and polyhydric alcohols and (2) a neutralized condensationproduct obtained with the aid of an alkaline catalyst from formaldehydein excess of the equimolecular proportion and a phenol having only twounsubstituted particularly reactive positions in the molecule, thecondensation product being capable of undergoing substantial furthercondensation when heated.

13. A process of producing soluble artificial resinous masses whichcomprises reacting together (1) an excess of a mixed ester obtained fromcitric and oleic acid on the one side and glycerine and benzylalcohol onthe other side, and (2) a neutralized condensation product obtained withthe aid of an alkaline catalyst from formaldehyde in excess of theequimolecular proportion and a mixture of oand pchlor mcresol, thecondensation product being capable of undergoing substantial furthercondensation HERBERT HGNEL.

